2-Butynylidenecyclohexane | 2807-13-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2-Butynylidenecyclohexane
• 英文别名: 4-Cyclohexyl-buten-(4)-in-(2)；But-2-ynylidenecyclohexane
• CAS: 2807-13-8
• 化学式: C₁₀H₁₄
• 分子量: 134.221
• InChiKey: VIXSEHLKFBCFDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-Butynylidenecyclohexane 在 氨 、 potassium amide 作用下， 以 乙醚 为溶剂， 生成 4-Cyclohexyl-buten-(3)-in-(1)
  参考文献：
  名称：

  van Boom,J.H. et al., Recueil des Travaux Chimiques des Pays-Bas, 1965, vol. 84, p. 813 - 820

  摘要：

  DOI：
• 作为产物：
  描述：

  cyclohexane (1-bromo-2-butynylidine) 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 0.33h， 以75%的产率得到2-Butynylidenecyclohexane
  参考文献：
  名称：

  Bromo[3]cumulene and bromo enyne radical cyclization to cyclopentenyne products

  摘要：

  DOI：

  10.1021/jo00296a085

文献信息

• Highly Regioselective Cobalt‐Catalyzed Hydroboration of Internal Alkynes
  作者：Yan‐Dong Zhang、Xiao‐Yu Li、Qian‐Kun Mo、Wen‐Bin Shi、Jia‐Bao Zhao、Shou‐Fei Zhu

  DOI：10.1002/anie.202208473

  日期：2022.9.5

  A highly selective hydroboration of unsymmetrical internal alkynes featuring unique regioselectivity, broad substrate scope and good functional group compatibility was realized by using cobalt catalysts modified with newly developed cyclopropane-based diphosphine ligands. The current protocol enabled the synthesis of novel alkenyl borates and improved the synthetic efficiency of bioactive compounds

  利用新开发的环丙烷基二膦配体修饰的钴催化剂，实现了不对称内炔烃的高选择性硼氢化反应，该反应具有独特的区域选择性、广泛的底物范围和良好的官能团相容性。目前的协议能够合成新的烯基硼酸盐，并提高了生物活性化合物的合成效率。
• ZIEGLER, CARL B. (JR), J. ORG. CHEM., 55,(1990) N, C. 2989-2986
  作者：ZIEGLER, CARL B. (JR)

  DOI：——

  日期：——
• Iron‐Catalyzed Allylic C(sp3)−H Silylation: Spin‐Crossover‐Efficiency‐Determined Chemoselectivity
  作者：Peng He、Mu‐Han Guan、Meng‐Yang Hu、Yuan‐Jun Zhou、Ming‐Yao Huang、Shou‐Fei Zhu

  DOI：10.1002/anie.202402044

  日期：2024.5.21

  The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C(sp3)−H silylation/alkyne hydrosilylation reaction, in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathway. Specifically, spin crossover led to alkyne hydrosilylation, whereas spin conservation resulted in a novel allylic C(sp3)−H silylation reaction. This chemoselectivity, governed by the spin‐crossover efficiency, reveals an unexpected dimension in spin effects and a first in the realm of transition‐metal‐catalyzed in situ silylation of allylic C(sp3)−H bonds, which had been previously inhibited by the heightened reactivity of alkenes in hydrosilylation reactions. Furthermore, this spin crossover can either accelerate or hinder the reaction at different stages within a single catalytic reaction, a phenomenon scarcely documented. Moreover, we identify a substrate‐assisted C−H activation mechanism, a departure from known ligand‐assisted processes, offering a fresh perspective on C−H activation strategies.